Polyacrylonitrile textile materials dyed with a quaternized benzothiazole azo dye



United States Patent 3,508,856 POLYACRYLONITRILE TEXTILE MATERIALS DYED WITH A QUATERNIZED BENZOTHI- AZOLE AZO DYE Hans Ruprecht Hensel, Heidelberg, and Magnus Rosenkranz, Ludwigshafen (Rhine), Germany, asslgnors to Badische Anilin- & Soda-Fabrik Aktiengesellschaft, Ludwigshafen (Rhine), Germany No Drawing. Filed Aug. 24, 1966, Ser. No. 574,565

Claims priority, applic211ti6o1r; gar-many, Mar. 10, 1966,

3 Int. Cl. C09b 27/00, 45/48; D06p 3/70 US. Cl. 8-41 3 Claims ABSTRACT OF THE DISCLOSURE The present invention relates to polyacrylonitrile textile material dyed with a dye having the formula:

in which X denotes a colorless anion.

It is known that polyacrylonitrile textile material may be dyed brilliant light-fast violet to blue shades by using basic benzothiazole azo dyes. These dyes have extremely high color strength and are fairly. easy to prepare. As a rule they have the disadvantage, however, that they give dyeings which have only moderate thermal fastness. High thermal fastness of polyacrylonitrile dyes is desirable however because the dyed textile material is in many cases pleated or ironed hot, i.e. exposed to great heat. If the thermal fastness is inadequate, the shade of the dyeings may change reversibly or irreversibly in an unwanted manner. Dyes of the anthraquinone series which are very resistant to the action of heat have therefore already been proposed which also give blue shades, although less brilliant. These dyes have a much lower color strength however than the blue basic azo dyes. In order to ensure similar color strength it is therefore necessary to use much larger amounts of anthraquinone dyes than of basic azo dyes.

The object of the present invention is to provide polyacrylonitrile textile material which has been dyed blue shades with basic azo dyes but which nevertheless has good thermal fastness.

This object is achieved with polyacrylonitrile textile material which contains 0.02 to 2% by weight, preferably 0.05 to 0.6% by weight, on the textile material, of a dye having the Formula I above.

In the said Formula I, X denotes any colorless anion of a simple or complex inorganic or organic acid. Examples of suitable anions are: C1 Br CH SO C H SO Zncl ZnBr C10 BF HSO 50, or PO Of these anions, CH SO, and C1 are preferred for technical reasons, but the type of anion is practically without influence on the properties of-the dye.

Examples of polyacrylonitrile materials are fibers, filaments, threads, flock, woven fabric or knitted fabric of polymers containing mainly polymerized acrylonitrile, for example to the extent of more than 85%. Such polymers may domain for example 95% of acrylonitrile units and about of methyl acrylate units; or 89% of acrylonitrile units, 6% of methylvinylpyridine units and 5% of vinyl acetate units; or 94% of acrylonitrile units, 5% of methylvinylpyridine units and 1% of vinyl acetate units.

3,508,856 Patented Apr. 28, 1970 The textile material which contains the dye having the Formula I may be obtained either by dyeing from a long liquor, for example at a liquor ratio of 40:1, padding with a short liquor, for example at a liquor ratio of 3:1 to 5:1, or printing with a print paste. The dye goes onto the fiber from a weakly acid medium, preferably an acetic acid medium.

The production of the dyed textile material may be carried out as follows:

The dye is made into a paste in a little water with an addition of the acid, for example acetic acid, formic acid, tartaric acid, boric acid, naphthalenesulfonic acid or sulphuric acid, and dissolved by pouring hot" water over it. It is also possible to add to the dye liquor subsequently, substances which produce acid during dyeing. Examples of these substances are salts of volatile bases with strong non-volatile acids, such as ammonium sulfate or water-soluble esters of organic acids which are hydrolyzed during dyeing. When using mineral acid solutions, these may be neutralized during the dyeing process by gradually adding alkali metal salts of weak acids, for example with sodium acetate. Dyeing may be carried out in an open vessel while boiling or in a closed vessel under pressure at temperatures higher than 100 C.

The dye having Formula I is prepared by conventional methods. For example 6-ethoxy-2-aminobenzothiazole may be diazotized, coupled with N-butyl-N-cyanoethylaniline and the coupling product methylated, or 6-methoxybenzothiazolone hydrazone may be coupled in the presence of an oxidizing agent with N-butyl-N-cyanoethylaniline. The anion in the dye thus obtained may be exchanged for another anion if desired. For example if the dye is obtained as the methosulfate by methylation with dimethyl sulfate, it is easy to prepare therefrom the corresponding hydrochloride.

Dyed textile materials obtained with the dye having the Formula I have a bright blue shade and high fastness to light, are fast to washing and are distinguished surprisingly by very good fastness to ironing. Furthermore the shade does not change in artificial light.

The invention is illustrated by the following examples. The parts in the examples are parts by weight.

EXAMPLE 1 0.1 part of the dye having the Formula I is made into a paste with 3 parts of acetic acid and dissolved by pouring 4000 parts of hot water over the paste. 6 parts of sodium acetate is added and 4 parts of a condensation product of 1 mole of oleyl alcohol with 15 moles of ethylene oxide, parts of polyacrylonitrile fibers are introduced into the dye liquor at 40 C., the latter is heated to 98 C. within thirty minutes and dyeing is continued for two hours in a boiling liquor. The dye liquor has been almost completely exhausted by this time. The material thus dyed is soaped for fifteen minutes in 5000 parts of water at 80 C; with an addition of 5 parts of a sulfonated fatty acid condensation product, rinsed and dried. The fibers show a deep blue shade having outstanding wash fastness, light fastness and very good thermal fastness.

The dye having the Formula I is prepared as follows: 180 parts of 2-amino-6-methoxybenzothiazole is dissolved in a mixture of 140 parts of 96% sulfuric acid and parts of ice and the resultant solution is poured into a mixture of 1900 parts of ice and 2900 parts of 95 sulfuric acid. 290 parts of nitrosylsulfuric acid (about 54% strength) is allowed to flow in during the course of two hours at 10 C. The diazo solution thus obtained is gradually coupled with a mixture of 212 parts of N- cyanoethyl-N-butylaniline, 5000 parts of water, 5000 parts of ice and 98 parts of sulfuric acid (96% When coupling is over, a solution of 2500 parts of sodium hydroxide in 50,000 parts of water is allowed to flow in and the product is suction filtered and dried at 60 C. The yield is 370 parts of coupling product.

To quaternize the coupling product, 370 parts thereof which has been dried and powdered is stirred in 1500 parts of chloroform and at 50 C. 141 parts of dimethyl sulfate is allowed to flow in during the course of three hours. The whole is boiled under reflux for three to four hours and the chloroform is distilled off with the simultaneous addition of 3000 parts of hot water. The dye, which is deposited in cooling, is suction filtered and dried at 50 C. The yield is 470 parts.

EXAMPLE 2 0.02 part of the dye having the Formula I is dissolved in 4000 parts of hot water. 2 parts of 80% acetic acid, parts of sodium sulfate and 3 parts of benzyltrimethyl ammonium chloride are added and at 40 C. 100 parts of polyacrylonitrile cloth is introduced into the dye liquor, heated within thirty minutes to 90 C. and dyed for fifteen minutes at this temperature. The whole is then heated to boiling temperature and dyed for another hour in boiling liquor. The material thus dyed is soaped for fifteen minutes in 5000 parts of water and 80 C. with an addition of 5 parts of a sulfonated fatty acid condensation product, rinsed and dried. A pale blue dyeing having excellent fastness to washing and light is obtained.

EXAMPLE 3 0.3 part of the dye having the Formula I is dissolved in 4000 parts of water and then parts of sodium sulfate, 2 parts of 98% sulfuric acid and 3 parts of a condensation product of 1 mole of octadecenol and moles of ethylene oxide are added. 100 parts of polyacrylonitrile cloth is introduced into the dye liquor at 50 C., heated within thirty minutes to 98 C. and dyed for two hours in a boiling liquor. The material thus dyed is soaped for fifteen minutes in 5000 parts of water at 80 C. with an addition of 5 parts of a sulfonated fatty acid condensation product, rinsed and dried. A deep blue dyeing is obtained having outstanding fastness to Washing, light and ironing.

EXAMPLE 4 Polyacrylonitrile cloth is printed with a dye paste which contains (in 1000 g.) 10 g. of the dye having the Formula I, 50 g. of thiodiethylene glycol, 50 g. of 30% acetic acid, 35 g. of tartaric acid, 35 g. of sodium chlorate (1:2), 160 g. of water, 220 g. of crystal gum thickening (1:2) and 440 g. of carboxymethylcellulose thickening (18%), dried and steamed at 0.5 atmosphere gauge. The cloth is then S CH30 /CHzCHz-CHz-CH3 X 162 CHrCHrC/N I CH3 in which X denotes a colorless anion.

2. Fibers of polyacrylonitrile materials which contain at least 89% by weight of acrylonitrile and have been dyed with 0.02 to 2% by weight of the dye having the formula:

CHz-CHz-OHs-CHa OHz-CHz-ON 41113 in which X denotes a colorless anion.

3. Fibers as claimed in claim 2 which have been dyed with 0.05 to 0.6% by Weight of said dye.

References Cited UNITED STATES PATENTS 4/1961 Merian et a1 841 4/ 1963 Fishwick et al 84l OTHER REFERENCES Derwents Belgium Patent Reports, Belg. Pat. 639,494, Badische Aniline, Received Patent Office May 1, 1964, 8-55 AB.

Derwents Belgium Patent Reports, No. 24/66, Belg. Pat. 673,532, Geigy S.A., received Patent Ofiice July 12, 1966, 8-55 AB.

NORMAN G. TORCHIN, Primary Examiner J. E. CALLAGHAN, Assistant Examiner US. Cl. X.R. 8177 Patent No. 1.5 8. 5 Dated Agril 28. 122;;

Inventor(s) R precht Hansel It: is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

"I In the references, insert 3,148,935 9/1964 Ptitzner 260-158--.

316mm sun-:0 :9 1-D Atteat:

Edward M. Flam Atteating Officor a m- L- or retontl 

